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CN105384898B - Waterborne polyurethane resin and preparation method thereof, cowboy's slurry - Google Patents

Waterborne polyurethane resin and preparation method thereof, cowboy's slurry Download PDF

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Publication number
CN105384898B
CN105384898B CN201510733472.2A CN201510733472A CN105384898B CN 105384898 B CN105384898 B CN 105384898B CN 201510733472 A CN201510733472 A CN 201510733472A CN 105384898 B CN105384898 B CN 105384898B
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parts
cowboy
slurry
weight
waterborne polyurethane
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CN105384898A (en
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代菊红
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Guangzhou dolphin New Material Co.,Ltd.
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Jiangmen Zhentu New Material Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D06M15/568—Reaction products of isocyanates with polyethers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D06M15/572—Reaction products of isocyanates with polyesters or polyesteramides

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses a kind of waterborne polyurethane resins, are reacted by 5~95 parts of macromolecule diol, 4~50 parts of diisocyanate, 0.1~9.7 part of low molecule polyol, 0.5~10.0 part of methylol acid, 0.5~27.6 part of low molecule active hydrogen compounds, 2.4~14.0 parts of aminated compounds, 0.5~2 part of neutralizer, 0.001~1 part of catalyst and 30~70 parts of deionized water and are obtained.The cowboy being prepared the invention also discloses the preparation method of the waterborne polyurethane resin and with the waterborne polyurethane resin starches.The present invention is by being modified waterborne polyurethane resin, improve the interior degree of cross linking of resin, it is improved to reach the cohesion of resin, the resin is recycled to prepare cowboy's slurry, cowboy slurry need not add auxiliary agent in use, it can be used with one-component, the auxiliary agent using toxic or inconvenient preservation is avoided, and the resistance to wash water effect of cowboy slurry is more excellent than traditional two-component cowboy slurry, and fastness greatly improves, 2 it is small when wash water after decalcomania do not fall off, keep original gloss, elasticity.

Description

Waterborne polyurethane resin and preparation method thereof, cowboy's slurry
Technical field
The present invention relates to a kind of waterborne polyurethane resin and preparation method thereof and with the waterborne polyurethane resin prepare and The cowboy's slurry obtained.
Background technology
At present, traditional cowboy slurry is all that two-component uses, and there are two types of common auxiliary agents, first, aziridines, one being isocyanide Esters of gallic acid.Aziridine auxiliary agent is toxic, belongs to national management and control, it is impossible to use；Another kind isocyanate is although nontoxic, but runs into air Easily solidification, it has not been convenient to preserve, production and application process is inconvenient.And if traditional cowboy slurry does not add auxiliary agent and cannot reach and washes Water requirement.Therefore, it is necessary to develop a kind of cowboy's slurry for not adding auxiliary agent.
The content of the invention
The object of the present invention is to provide a kind of waterborne polyurethane resins of modification.
It is a further object of the present invention to provide the preparation methods of the waterborne polyurethane resin.
It is a further object of the present invention to provide a kind of cowboy's slurries being prepared with the waterborne polyurethane resin.
One of in order to achieve the above objectives, the present invention uses following technical scheme：
Waterborne polyurethane resin, according to parts by weight, by 5~95 parts of macromolecule diol, 4~50 parts of diisocyanate Ester, 0.1~9.7 part of low molecule polyol, 0.5~10.0 part of methylol acid, 0.5~27.6 part of low molecular work Sprinkle hydrogen compound, 2.4~14.0 parts of aminated compounds, 0.5~2 part of neutralizer, 0.001~1 part of catalyst and 30~ 70 parts of deionized water is reacted and obtained.
Further, the macromolecule diol is the dihydric alcohol that average molecular weight is 500~10000.
Further, the macromolecule diol is for polyester diol, polyesteramide dihydric alcohol, polyether Glycols, poly- At least one of ether-ether glycol and polycarbonate glycol.
Further, the diisocyanate is aromatic diisocyanate, aliphatic diisocyanate and alicyclic two At least one of isocyanates.
Further, the diisocyanate is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, isophorone Diisocyanate, hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate, paraphenylene diisocyanate, Isosorbide-5-Nitrae-hexamethylene Alkane diisocyanate, six methylene of benzene dimethylene diisocyanate, cyclohexanedimethyleterephthalate diisocyanate and trimethyl -1,6- At least one of group diisocyanate.
Further, the low molecule polyol is ethylene glycol, 1,4-butanediol, dipropylene glycol, 1,2- Propylene glycol, neopentyl glycol, methyl propanediol, 1,6- hexylene glycols, diethylene glycol (DEG), 1,3-PD, 1,5-PD, 3- methyl-1s, 5- pentanediols, 1,8- ethohexadiols, 1,9- nonanediols, trimethylolpropane, glycerine, 1,2,6- hexanetriols, pentaerythrite, three ethyl alcohol At least one of amine and diethanol amine；Most preferred low molecule polyol is hydroxymethyl-propane, glycerine, 1,2,6- oneself At least one of triol, pentaerythrite and triethanolamine.
Further, the methylol acid be methylol formic acid, methylol acetic acid, hydroxymethyl propionic acid, dihydroxymethyl formic acid, At least one of dihydroxymethyl acetic acid, dihydromethyl propionic acid and dimethylolpropionic acid.
Further, the low molecule active hydrogen compounds is polyacrylate polyol, polyolefin polyhydric alcohol, vegetable oil At least one of polyalcohol, amine terminated polyether and epoxy resin.
Further, the aminated compounds is that molar ratio is 1.1~17.1：1 diamine and the composition of monoamine.
Further, the aminated compounds is that molar ratio is 1.5~9.6：1 diamine and the composition of monoamine.
Further, the diamine is in binary primary amine, binary secondary amine while diamine containing primary amine groups and secondary amine At least one；The monoamine is unitary secondary amine.
Further, the binary primary amine be in aliphatic primary diamines, cycloaliphatic primary diamines, Aromatic primary diamines at least It is a kind of.
Further, the aliphatic primary diamines are ethylenediamine, 1,3- propane diamine, 1,2- propane diamine, dimethyl -1,3- third Diamines, Putriscine, 1,3- butanediamine, 1,2- butanediamine, 1,5- pentanediamines, 1,6- hexamethylene diamines, 1,7- heptamethylene diamines, 1,8- are pungent In diamines, 1,10- decamethylene diamines, 1,12- dodecyls diamines, 2,5- dimethyl -2,5- hexamethylene diamine and N- isopropyl ethylenediamines It is at least one.
Further, the cycloaliphatic primary diamines be 1,2- cyclohexanediamine, it is 1,3- cyclohexanediamine, Isosorbide-5-Nitrae-cyclohexanediamine, different Isophoronediamine, 2,4- diethyl -6- methyl-1s, 3- cyclohexanediamine, 4,6- diethyl -2- methyl-1s, 3- cyclohexanediamine, 1,3- At least one of hexamethylene two (methylamine) and Isosorbide-5-Nitrae-hexamethylene double (methylamines).
Further, the Aromatic primary diamines are in 3,4- toluenediamines, p-phenylenediamine, m-phenylene diamine (MPD) and o-phenylenediamine At least one.
Further, the binary secondary amine is N, N- diisopropyl ethylenediamines, N, N- bis- (3,3- dimethyl -2- butyl) - 1,6- diamino hexane, N, N- di-sec-butyls -1,2- diaminopropanes, N, N- bis- (2- cyclobutenyls) -1,3- diaminobutanes, N, N- bis- (1- cyclopropylethyls) -1,5- 1,5-DAPs, N, N- di-sec-butyls -1,6- diamino hexane, (the 1- cyclobutyl of N, N- bis- Ethyl) at least one of-Isosorbide-5-Nitrae-diaminocyclohexane and N, N- di-sec-butyl -1,8- diamino-octane.
Further, described while containing primary amine groups and secondary amine diamines are N- isopropyls ethylenediamine, N- sec-butyl -1, 2- diaminopropanes, N- isopropyls propane diamine, N- sec-butyls -1,2- diaminobutane, N-2- cyclobutenyl -1,3- diamino fourths Alkane, N-1- cyclopropylethyls -1,5- 1,5-DAP, N- sec-butyls -1,6- diamino hexane, N- cyclobutylethyl-Isosorbide-5-Nitrae-two At least one of aminocyclohexane, N- sec-butyl -1,8- diamino-octanes.
Further, the unitary secondary amine be dimethylamine, it is diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, two different At least one of butylamine, two n-octyl amines, two n-hexylamines and dicyclohexyl amine；Most preferred unitary secondary amine is diethylamine, diisopropyl At least one of amine, di-n-butylamine and dicyclohexyl amine.
Further, the neutralizer is triethylamine, sodium hydroxide, potassium hydroxide, sodium acid carbonate, sodium acetate, pyrophosphoric acid At least one of sodium, sodium carbonate and ammonium hydroxide.
Further, the catalyst is bismuth class or tin catalyst.
Further, the bismuth class catalyst is organo-bismuth class catalyst and/or bismuth zinc mixed catalyst.
Further, the bismuth class catalyst is bismuth carboxylate.
Further, the tin catalyst is dibutyl tin laurate, stannous octoate, two (dodecyl sulphur) two fourths At least one in Ji Xi, dibutyltin diacetate, dialkyl tin dimaleate, two mercaptan dialkyl tins and mercaptan dioctyl tin Kind.
Further, the number-average molecular weight of the waterborne polyurethane resin is 10000~50000, total amine value for 10.0~ 16.0mgKOH/g, primary amine value are the 3.1~40.0% of total amine value；Secondary amine value is the 2.0~84.5% of total amine value；Tertiary amine value is The 2.9~55.6% of total amine value.
The preparation method of waterborne polyurethane resin described in any one of front, comprises the following steps：
(1) macromolecule diol and diisocyanate are mixed, adds catalyst, reacted 2~8h at 30~100 DEG C, obtain Performed polymer；
(2) low molecule active hydrogen compounds, methylol acid, low molecule polyol are added in, reacts 3 at 70~80 DEG C ~5h；
(3) less than 60 DEG C are cooled to, neutralizer stirring is added in, continues to be cooled to less than 30 DEG C, is added under stirring condition pre- The deionized water first cooled down；
(4) add in aminated compounds, carry out chain extension and chain termination reaction to get.
A kind of cowboy's slurry, including the waterborne polyurethane resin described in any one of front.
A kind of preparation method of cowboy's slurry, according to weight fraction, by the waterborne polyurethane resin described in any one of front 60 parts, 30 parts of titanium dioxide, 0.3 part of dispersant, 3 parts of moisturizer progress high speed dispersions, fineness of dispersion adds increasing below 50 μm Until thick dose adjusts viscosity as 120000~140000cps, cowboy's slurry is made.
The invention has the advantages that：
The present invention improves the interior degree of cross linking of resin, to reach the interior of resin by being modified to waterborne polyurethane resin Poly- property improves, and the resin is recycled to prepare cowboy's slurry, and cowboy slurry need not add auxiliary agent in use, can be with one-component It uses, avoids the auxiliary agent using toxic or inconvenient preservation, and the resistance to wash water effect of cowboy slurry is than traditional double groups Part cowboy slurry is more excellent, and fastness greatly improves, 2 it is small when wash water after decalcomania do not fall off, keep original gloss, elasticity.
Specific embodiment
With reference to specific embodiment, the present invention is described further：
Prepare the universal method of cowboy's slurry：By 60 parts by weight of waterborne polyurethane resin, 30 parts by weight of titanium dioxide, dispersant 0.3 parts by weight, 3 parts by weight of moisturizer carry out high speed dispersion, and below 50 μm, add thickener adjusting viscosity is fineness of dispersion Until 120000~140000cps, cowboy's slurry is made.
Embodiment 1
Waterborne polyurethane resin is prepared according to following steps：
(1) polyester two that 95 parts by weight molecular weight are 10000 is packed into the four-hole boiling flask equipped with mixer, thermometer The dibutyl tin laurate of the hexamethylene diisocyanate and 0.05 parts by weight of first alcohol and 4 parts by weight, under stream of nitrogen gas With 90 DEG C heat preservation 6 it is small when, performed polymer is made；
(2) 1,4-butanediol, the 0.5 parts by weight hydroxyl value for adding in 0.1 parts by weight are polynary for the vegetable oil of 163mgKOH/g The dihydromethyl propionic acid of alcohol and 2.5 parts by weight, when 75 DEG C of insulation reactions 4 are small；
(3) less than 60 DEG C are cooled to, adds in the triethylamine of 2 parts by weight, stirs 30 minutes, continues to be cooled to less than 30 DEG C, Under high velocity agitation, add in and be previously cooled to less than 5 DEG C, the deionized water of 30 parts by weight；
(4) 1.2 parts by weight (0.016mol) methanediamine, 1.2 parts by weight (0.016mol) dimethylamine are added, at 25~30 DEG C Make its react 30 minutes, be warming up to 70 DEG C of insulation reactions 3 it is small when.
The resin solid content of the polyurethane resin solution A so obtained be 40.2wt%, number-average molecular weight 8000, total amine It is worth for 8.0mgKOH/g, primary amine value 4.2mgKOH/g, secondary amine value 1.1mgKOH/g, tertiary amine value 2.6mgKOH/g；Then Obtained waterborne polyurethane resin solution A is made cowboy and starches A by the preparation method according to cowboy's slurry.
Embodiment 2
Waterborne polyurethane resin is prepared according to following steps：
(1) polyethers two that 93 parts by weight molecular weight are 10000 is packed into the four-hole boiling flask equipped with mixer, thermometer The stannous octoate of the toluene di-isocyanate(TDI) and 0.05 parts by weight of first alcohol and 10 parts by weight, with 30 DEG C of heat preservations 8 under stream of nitrogen gas Hour, performed polymer is made；
(2) trimethylolpropane, the 0.5 parts by weight hydroxyl value for adding in 1 parts by weight are polynary for the vegetable oil of 163mgKOH/g The dihydromethyl propionic acid of alcohol and 2.5 parts by weight, when 75 DEG C of insulation reactions 4 are small；
(3) be cooled to less than 60 DEG C, add in the triethylamine of 1.5 parts by weight, stir 30 minutes, continue to be cooled to 30 DEG C with Under, under high velocity agitation, addition is previously cooled to less than 5 DEG C, the deionized water of 70 parts by weight；
(4) 1.7 parts by weight (0.0283mol) ethylenediamine, 0.7 parts by weight (0.0029mol), two n-octyl amine are added, at 25 DEG C ~30 DEG C make its react 30 minutes, be warming up to 70 DEG C of insulation reactions 3 it is small when.
The resin solid content of the polyurethane resin solution B so obtained be 40.1wt%, number-average molecular weight 10000, always Amine value is 10.0mgKOH/g, primary amine value 5.7mgKOH/g, secondary amine value 3.8mgKOH/g, tertiary amine value 0.5mgKOH/g；So Cowboy is made in obtained polyurethane resin solution B according to the preparation method of cowboy's slurry afterwards and starches B.
Embodiment 3
Waterborne polyurethane resin is prepared according to following steps：
(1) polyether ester that 90 parts by weight molecular weight are 10000 is packed into the four-hole boiling flask equipped with mixer, thermometer The isooctyl acid bismuth of the hexamethylene diisocyanate and 0.05 parts by weight of dihydric alcohol and 6 parts by weight, with 90 DEG C under stream of nitrogen gas Keep the temperature 6 it is small when, performed polymer is made；
(2) 0.4 parts by weight of glycerin is added in, the vegetable oil polyol and 2.5 weights that 1.0 parts by weight hydroxyl values are 163mgKOH/g The dihydromethyl propionic acid of part is measured, when 75 DEG C of insulation reactions 4 are small；
(3) be cooled to less than 60 DEG C, add in the triethylamine of 1.0 parts by weight, stir 30 minutes, continue to be cooled to 30 DEG C with Under, under high velocity agitation, addition is previously cooled to less than 5 DEG C, the deionized water of 40 parts by weight；
(4) 2.0 parts by weight (0.0333mol) ethylenediamine, 0.6 parts by weight (0.0046mol) di-n-butylamine are added, at 25 DEG C ~30 DEG C make its react 30 minutes, be warming up to 70 DEG C of insulation reactions 3 it is small when.
The resin solid content of the polyurethane resin solution C so obtained be 40.0wt%, number-average molecular weight 19000, always Amine value is 12.0mgKOH/g, primary amine value 5.0mgKOH/g, secondary amine value 6.2mgKOH/g, tertiary amine value 0.8mgKOH/g；So Cowboy is made in obtained polyurethane resin solution C according to the preparation method of cowboy's slurry afterwards and starches C.
Embodiment 4
Waterborne polyurethane resin is prepared according to following steps：
(1) the poly- carbonic acid that 62 parts by weight molecular weight are 1500 is packed into the four-hole boiling flask equipped with mixer, thermometer The dibutyltin diacetate of trimethyl -1, the 6- hexamethylene diisocyanate and 0.05 parts by weight of esterdiol and 18 parts by weight, Under stream of nitrogen gas with 70 DEG C heat preservation 5 it is small when, performed polymer is made；
(2) add in the pentaerythrites of 4.5 parts by weight, the polyolefin polyhydric alcohol that 10 parts by weight hydroxyl values are 163mgKOH/g and The dihydromethyl propionic acid of 2.5 parts by weight, when 75 DEG C of insulation reactions 4 are small；
(3) be cooled to less than 60 DEG C, add in the triethylamine of 1.5 parts by weight, stir 30 minutes, continue to be cooled to 30 DEG C with Under, under high velocity agitation, addition is previously cooled to less than 5 DEG C, the deionized water of 60 parts by weight；
(4) add by 1,6- hexamethylene diamines, 4.3 parts by weight (0.037mol), 1.2 parts by weight of di-n-butylamine (0.0093mol), Make at 25~30 DEG C its react 30 minutes, be warming up to 70 DEG C of insulation reactions 3 it is small when.
The resin solid content of the polyurethane resin solution D so obtained be 40.1wt%, number-average molecular weight 28000, always Amine value is 14.0mgKOH/g, primary amine value 1.6mgKOH/g, secondary amine value 10.8mgKOH/g, tertiary amine value 1.6mgKOH/g； Then cowboy is made in obtained polyurethane resin solution D according to the preparation method of cowboy's slurry and starches D.
Embodiment 5
Waterborne polyurethane resin is prepared according to following steps：
(1) be packed into the four-hole boiling flask equipped with mixer, thermometer 55 parts by weight molecular weight be 2000 gather oneself in The dibutyl tin laurate of the isophorone diisocyanate and 0.05 parts by weight of ester dihydric alcohol and 25 parts by weight, in nitrogen gas Flow down with 80 DEG C heat preservation 4 it is small when, performed polymer is made；
(2) adding in 1.3 parts by weight, 1,2,6- hexanetriol, 1.3 parts by weight trimethylolpropanes, 9.4 parts by weight hydroxyl values is The dihydromethyl propionic acid of the vegetable oil polyol of 163mgKOH/g and 2.5 parts by weight, when 75 DEG C of insulation reactions 4 are small；
(3) be cooled to less than 60 DEG C, add in the triethylamine of 1.2 parts by weight, stir 30 minutes, continue to be cooled to 30 DEG C with Under, under high velocity agitation, addition is previously cooled to less than 5 DEG C, the deionized water of 50 parts by weight；
(4) 7.35 parts by weight (0.0433mol) isophorone diamine, 0.65 parts by weight (0.0089mol) diethylamine are added Solution, make at 25~30 DEG C its react 30 minutes, be warming up to 70 DEG C of insulation reactions 3 it is small when.
The resin solid content of the polyurethane resin solution E so obtained be 40.3wt%, number-average molecular weight 31000, always Amine value is 16.0mgKOH/g, primary amine value 1.8mgKOH/g, secondary amine value 12.7mgKOH/g, tertiary amine value 1.5mgKOH/g； Then cowboy is made in obtained polyurethane resin solution E according to the preparation method of cowboy's slurry and starches E.
Embodiment 6
Performance test：Cowboy's slurry that Examples 1 to 5 is obtained starches the parallel contrast test of progress, detection knot with traditional cowboy Fruit is as shown in the table：
Note：Had after not by representing wash water slurry come off, the unqualified phenomenon such as alice.
From testing result：After graphite+ferment wash water 2h, cowboy of the invention starches decalcomania and does not fall off, and keeps former It is glossy, elastic, it was demonstrated that its fastness starches higher than traditional cowboy, and without adding other auxiliary agents.
Embodiment 7
Waterborne polyurethane resin is prepared according to following steps：
(1) makrolon that 5 parts by weight molecular weight are 1000 is packed into the four-hole boiling flask equipped with mixer, thermometer The bismuth carboxylate of the benzene dimethylene diisocyanate and 1 parts by weight of glycol and 5 parts by weight, with 50 DEG C of heat preservations 5 under stream of nitrogen gas Hour, performed polymer is made；
(2) 9.7 parts by weight triethanolamines are added in, the amine terminated polyether and 10 that 27.6 parts by weight hydroxyl values are 170mgKOH/g The dimethylolpropionic acid of parts by weight, when 70 DEG C of insulation reactions 5 are small；
(3) be cooled to less than 60 DEG C, add in the sodium acid carbonate of 0.5 parts by weight, stir 30 minutes, continue to be cooled to 30 DEG C with Under, under high velocity agitation, addition is previously cooled to less than 5 DEG C, the deionized water of 50 parts by weight；
(4) 5 parts by weight N- isopropyls ethylenediamines, 3 parts by weight dicyclohexyl amine solution are added, it is made to react 30 at 25~30 DEG C Minute, be warming up to 70 DEG C of insulation reactions 3 it is small when.
Cowboy's slurry will be made in the preparation method that obtained polyurethane resin solution is starched according to cowboy.
Embodiment 8
Waterborne polyurethane resin is prepared according to following steps：
(1) polyether ester that 25 parts by weight molecular weight are 5000 is packed into the four-hole boiling flask equipped with mixer, thermometer The bismuth carboxylate of the cyclohexanedimethyleterephthalate diisocyanate and 0.001 parts by weight of glycol and 50 parts by weight, under stream of nitrogen gas with When 100 DEG C of heat preservations 2 are small, performed polymer is made；
(2) 7.2 parts by weight pentaerythrites are added in, the epoxy resin and 7.5 that 15.2 parts by weight hydroxyl values are 150mgKOH/g The hydroxymethyl propionic acid of parts by weight, when 80 DEG C of insulation reactions 3 are small；
(3) be cooled to less than 60 DEG C, add in the sodium hydroxide of 0.8 parts by weight, stir 30 minutes, continue to be cooled to 30 DEG C with Under, under high velocity agitation, addition is previously cooled to less than 5 DEG C, the deionized water of 50 parts by weight；
(4) 8 parts by weight N, N- diisopropyl ethylenediamines, 6 parts by weight di-iso-butylmanice solution are added, make it anti-at 25~30 DEG C Answer 30 minutes, be warming up to 70 DEG C of insulation reactions 3 it is small when.
Cowboy's slurry will be made in the preparation method that obtained polyurethane resin solution is starched according to cowboy.
The above description is merely a specific embodiment, but protection scope of the present invention is not limited thereto, any Belong to those skilled in the art in the technical scope disclosed by the present invention, the change or replacement that can be readily occurred in all should It is included within the scope of the present invention.Therefore, protection scope of the present invention should be subject to the protection scope in claims.

Claims (7)

1. a kind of cowboy slurry, which is characterized in that according to parts by weight, by 60 parts of waterborne polyurethane resins, 30 parts of titanium dioxides, 0.3 part of dispersant, 3 parts of moisturizer are prepared；
Wherein, the waterborne polyurethane resin, according to parts by weight, by 5~95 parts of macromolecule diol, 4~50 parts Diisocyanate, 0.1~9.7 part of low molecule polyol, 0.5~10.0 part of methylol acid, 0.5~27.6 part Low molecule active hydrogen compounds, 2.4~14.0 parts of aminated compounds, 0.5~2 part of neutralizer, 0.001~1 part of catalysis Agent and 30~70 parts of deionized water are reacted and obtained；
The low molecule active hydrogen compounds is polyacrylate polyol, polyolefin polyhydric alcohol, vegetable oil polyol, Amino End Group At least one of polyethers and epoxy resin；The low molecule polyol is ethylene glycol, 1,4-butanediol, a contracting dipropyl Glycol, 1,2-PD, neopentyl glycol, methyl propanediol, 1,6- hexylene glycols, diethylene glycol (DEG), 1,3-PD, 1,5-PD, 3- methyl-1s, 5- pentanediols, 1,8- ethohexadiols, 1,9- nonanediols, trimethylolpropane, glycerine, 1,2,6- hexanetriols, Ji Wusi At least one of alcohol, triethanolamine and diethanol amine.
2. cowboy's slurry according to claim 1, which is characterized in that the macromolecule diol is that average molecular weight is 500 ~10000 dihydric alcohol.
3. cowboy's slurry according to claim 2, which is characterized in that the macromolecule diol is for polyester diol, gathers At least one of esteramides dihydric alcohol, polyether Glycols, polyethers esterdiol and polycarbonate glycol.
4. cowboy's slurry according to claim 1, which is characterized in that the methylol acid is methylol formic acid, methylol second At least one in acid, hydroxymethyl propionic acid, dihydroxymethyl formic acid, dihydroxymethyl acetic acid, dihydromethyl propionic acid and dimethylolpropionic acid Kind.
5. cowboy's slurry according to claim 1, which is characterized in that the aminated compounds is that molar ratio is 1.1~17.1： 1 diamine and the composition of monoamine.
6. cowboy according to claim 1 slurry, which is characterized in that the number-average molecular weight of the waterborne polyurethane resin is 10000~50000, total amine value is 10.0~16.0mgKOH/g, and primary amine value is the 3.1~40.0% of total amine value；Secondary amine value is total The 2.0~84.5% of amine value；Tertiary amine value is the 2.9~55.6% of total amine value.
7. cowboy according to claim 1 slurry, which is characterized in that the preparation method of the waterborne polyurethane resin include with Lower step：
(1) macromolecule diol and diisocyanate are mixed, adds catalyst, reacted 2~8h at 30~100 DEG C, obtain pre-polymerization Body；
(2) low molecule active hydrogen compounds, methylol acid, low molecule polyol are added in, react 3 at 70~80 DEG C~ 5h；
(3) less than 60 DEG C are cooled to, neutralizer stirring is added in, continues to be cooled to less than 30 DEG C, is added under stirring condition cold in advance But deionized water；
(4) add in aminated compounds, carry out chain extension and chain termination reaction to get.
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CN102532451A (en) * 2010-12-31 2012-07-04 四川国和新材料有限公司 Amine composition and application thereof, polyurethane resin and preparation method and application thereof
CN102702466A (en) * 2012-06-20 2012-10-03 温州市宏得利树脂有限公司 Preparation method of aqueous polyurethane emulsion for synthetic leather
CN103232584A (en) * 2013-04-23 2013-08-07 东莞长联新材料科技股份有限公司 High-performance environment-friendly type water-borne polyurethane and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102532451A (en) * 2010-12-31 2012-07-04 四川国和新材料有限公司 Amine composition and application thereof, polyurethane resin and preparation method and application thereof
CN102702466A (en) * 2012-06-20 2012-10-03 温州市宏得利树脂有限公司 Preparation method of aqueous polyurethane emulsion for synthetic leather
CN103232584A (en) * 2013-04-23 2013-08-07 东莞长联新材料科技股份有限公司 High-performance environment-friendly type water-borne polyurethane and preparation method thereof

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